CN105646364A - Synthesis method of imidazole-4-methyl formate based on ionic liquid - Google Patents
Synthesis method of imidazole-4-methyl formate based on ionic liquid Download PDFInfo
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- CN105646364A CN105646364A CN201610113398.9A CN201610113398A CN105646364A CN 105646364 A CN105646364 A CN 105646364A CN 201610113398 A CN201610113398 A CN 201610113398A CN 105646364 A CN105646364 A CN 105646364A
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention provides a synthesis method of imidazole-4-methyl formate based on an ionic liquid. The synthesis method is characterized by comprising steps as follows: (1) the ionic liquid and acetyl methyl formate are added to a three-neck flask provided with a stirring and backflow device and stirred at the constant temperature, sodium ethoxide is slowly and dropwise added under the condensation and reflux conditions, the mixture is stirred at the constant temperature, formamide and sulfuric acid are added, the mixture is heated and stirred until a reaction is completed and then is cooled to the room temperature, and an intermediate product is obtained; (2) an ethanol solution is added to the intermediate product prepared in the step (1) and mixed uniformly, a hydrogen dioxide solution is dropwise added, the mixture is stirred to react and left to stand, the ionic liquid is separated through distillation under the reduced pressure, suction filtration is performed on remaining substances, the remaining substances are washed to be neutral and then dried, and imidazole-4-methyl formate based on the ionic liquid is obtained. The process for synthesizing imidazole-4-methyl formate is simple, imidazole-4-methyl formate is synthesized in one step, the reaction time is short, the yield is high, no pollution is caused to the environment, aftertreatment and purification are simple and convenient, and industrial production is facilitated.
Description
Technical field:
The invention belongs to medicinal chemistry art, be specifically related to the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid.
Background technology:
Along with the development of heterocyclic chemistry, the concern of the synthesis of imidazole and its derivants and applied research are increasingly subject to chemical research person. Imidazoles is containing five yuan of fragrant heterocompounds of position nitrogen-atoms between two in molecular structure, and nitrogen-atoms has the sp2 lone pair electrons of non-Cheng Jian and five yuan of structures also, and therefore it has armaticity, soda acid both sexes, complex coordination. The compound of imidazole ring-containing plays very important effect on medicine synthesizes, and can be used for producing the medicines such as treatment heart disease, anemia, rheumatism, arthritis and digestive tract ulcer, thus attention always. And imidazoles or important fine chemical material, imidazole and its derivants is all widely used in differentiation agents, surfactant, synthetic material field.
In recent years; the synthesis of imdazole derivatives and the research of application is very active; as the imidazole formic acid methyl ester that replaces sarcosine and glycine can be combined and obtain N-Methylimidazole. methyl formate as raw material by esterification, N-formylated, cyclization, selectivity desulfuration, or using methyl bromoacetate as the Material synthesis N-imidazole formic acid methyl ester replaced. Imidazolyl carboxylic acid ester is the precursor of synthesis histidine, has critically important practical value, but the report being based on this aspect is very rare in organic synthesis.
Disclosed in China's document " preparation of 4-imidazole-ethyl formate; Ma Jimei etc.; University Of Suzhou's journal (natural science edition), the 21st volume the 1st phase, 58-61 page; publication date in January, 2005 ", the preparation method of 4-imidazole formic acid methyl ester is: employing glycine is raw material; by acidylate, esterification, with Ethyl formate condensation under NaH effect, then with KSCN cyclization; thin base is sloughed in oxidation, obtains product. This design route is relatively simple, and raw material economics is easy to get, easy to operate, but productivity ratio is relatively low, it is difficult to for actual production.
The material that ionic liquid is in a liquid state in room temperature or near room temperature, is made up of ion completely, ionic liquid is not equivalent to electrolyte solution, this solution does not have electroneutral molecule, is made up of anion and cation completely, greatly extend the range of application of classical fused salt.Ionic liquid is environmental protection not only, and has very big using value in frontiers such as functional material, the energy, resource environment, life sciences.
The present invention is on the basis of existing technology, adds ionic liquid in imidazolyl carboxylic acid ester preparation technology, utilizes the property of ionic liquid, optimized fabrication technique, adopts one-step synthesis method imidazoles-4-methyl formate, and improve productivity.
Summary of the invention:
The present invention to solve technical problem originally and be to provide the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid, select hydrophobic ionic liquid as reaction system, one-step synthesis method imidazoles-4-methyl formate, technique is simple, yield is high, and green non-pollution, ionic liquid recoverable, reduce production cost, be conducive to industrialized production.
For solving this above-mentioned technical problem, the technical scheme is that
A kind of synthetic method of the imidazoles-4-methyl formate based on ionic liquid, it is characterised in that: comprise the following steps:
(1)
In the there-necked flask with stirring and reflux, adding ionic liquid and acetyl formic acid methyl ester, constant temperature stirs, be slowly added dropwise Sodium ethylate when condensing reflux, constant temperature stirs, and adds Methanamide and sulphuric acid, heated and stirred, to having reacted, is cooled to room temperature, obtains intermediate product;
(2) intermediate product step (1) prepared adds alcoholic solution, mix homogeneously, dropping hydrogenperoxide steam generator, stirring reaction, stand, decompression separated go out ionic liquid, then by surplus materials sucking filtration, be washed to neutrality, washing and drying, obtain the imidazoles-4-methyl formate based on ionic liquid.
Preferred as technique scheme, in described step (1), ionic liquid is hydrophobic type ionic liquid.
Preferred as technique scheme, in described step (1), the pyridylium that ionic liquid is alkyl-quaternaryammonium cations or N-alkyl replaces.
Preferred as technique scheme, in described step (1), the temperature of constant temperature stirring is 6-10 DEG C, and the time is 30-90min.
Preferred as technique scheme, in described step (1), the temperature of heated and stirred is 100-110 DEG C, and the time is 2-4h.
Preferred as technique scheme, in described step (1), the volume ratio of ionic liquid, acetyl formic acid methyl ester, Sodium ethylate, Methanamide and sulphuric acid is 5-8:2-4:1-2:2-3:1-3.
Preferred as technique scheme, in described step (2), intermediate product, ethanol, hydrogenperoxide steam generator volume ratio be 1:3-6:2-4.
Preferred as technique scheme, in described step (2), the concentration of hydrogenperoxide steam generator is 30-50%.
Preferred as technique scheme, in described step (2), the temperature of stirring reaction is 45-50 DEG C.
With prior art with than, the method have the advantages that
Synthetic method disclosed by the invention and traditional synthetic method with than, select hydrophobic ionic liquid as reaction system, ionic liquid and ordinary solvent with than, stable performance, gentleer with ratio with traditional solvent, more promote reaction, and reaction efficiency is higher, recoverable, environmental protection, mental retardation is efficient, based on ionic liquid, it is possible to one-step synthesis imidazoles-4-methyl formate, technique is simple, reduces technology difficulty, and yield is high, reduce production cost, be conducive to industrialized production.
Detailed description of the invention:
Describing the present invention in detail below in conjunction with specific embodiment, illustrative examples and explanation in this present invention are used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the hydrophobic type alkyl-quaternaryammonium cations liquid of 5 parts and the acetyl formic acid methyl ester of 2 parts, 6 DEG C of constant temperature stirring 30min, the Sodium ethylate of 1 part it is slowly added dropwise when condensing reflux, 6 DEG C of constant temperature stirring 30min, adding the Methanamide of 2 parts and the sulphuric acid of 1 part, 100 DEG C of heated and stirred 2h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 3 parts, mix homogeneously, drip the hydrogenperoxide steam generator of the 30-% of 2 parts, 45 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 2:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the pyridylium liquid of the hydrophobic type N-alkyl replacement of 8 parts and the acetyl formic acid methyl ester of 4 parts, 10 DEG C of constant temperature stirring 90min, the Sodium ethylate of 2 parts it is slowly added dropwise when condensing reflux, 10 DEG C of constant temperature stirring 90min, adding the Methanamide of 3 parts and the sulphuric acid of 3 parts, 110 DEG C of heated and stirred 4h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 6 parts, mix homogeneously, drip 4 parts 50% hydrogenperoxide steam generator, 50 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 3:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the hydrophobic type alkyl-quaternaryammonium cations liquid of 6 parts and the acetyl formic acid methyl ester of 2-4 part, 7 DEG C of constant temperature stirring 60min, the Sodium ethylate of 1.5 parts it is slowly added dropwise when condensing reflux, 8 DEG C of constant temperature stirring 60min, adding the Methanamide of 2.5 parts and the sulphuric acid of 2 parts, 105 DEG C of heated and stirred 3h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 4 parts, mix homogeneously, drip 3 parts 40% hydrogenperoxide steam generator, 47 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 4:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the pyridylium liquid of the N-alkyl replacement of 7 parts and the acetyl formic acid methyl ester of 2.5 parts, 8 DEG C of constant temperature stirring 50min, the Sodium ethylate of 1.6 parts it is slowly added dropwise when condensing reflux, 8 DEG C of constant temperature stirring 50min, adding the Methanamide of 2.1 parts and the sulphuric acid of 1.8 parts, 100 DEG C of heated and stirred 2.5h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 4 parts, mix homogeneously, drip 2.5 parts 35% hydrogenperoxide steam generator, 42 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 5:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the pyridylium liquid of the hydrophobic type N-alkyl replacement of 8 parts and the acetyl formic acid methyl ester of 2.5 parts, 10 DEG C of constant temperature stirring 30min, the Sodium ethylate of 1 part it is slowly added dropwise when condensing reflux, 10 DEG C of constant temperature stirring 30min, adding the Methanamide of 3 parts and the sulphuric acid of 1 part, 110 DEG C of heated and stirred 2h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 6 parts, mix homogeneously, drip 2 parts 50% hydrogenperoxide steam generator, 50 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 6:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the pyridylium liquid of the N-alkyl replacement of 5 parts and the acetyl formic acid methyl ester of 4 parts, 6 DEG C of constant temperature stirring 90min, the Sodium ethylate of 2 parts it is slowly added dropwise when condensing reflux, 6 DEG C of constant temperature stirring 90min, adding the Methanamide of 2 parts and the sulphuric acid of 3 parts, 100 DEG C of heated and stirred 4h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 3 parts, mix homogeneously, drip 4 parts 30% hydrogenperoxide steam generator, 45 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
Embodiment 7:
(1)
By volume part meter, in the there-necked flask with stirring and reflux, add the hydrophobic type alkyl-quaternaryammonium cations liquid of 6 parts and the acetyl formic acid methyl ester of 3 parts, 6 DEG C of constant temperature stirring 60min, the Sodium ethylate of 1.2 parts it is slowly added dropwise when condensing reflux, 6 DEG C of constant temperature stirring 60min, adding the Methanamide of 2.4 parts and the sulphuric acid of 1.2 parts, 100 DEG C of heated and stirred 3h, to having reacted, it is cooled to room temperature, obtains intermediate product.
(2) by volume part is counted, the intermediate product of 1 part step (1) prepared adds the alcoholic solution of 6 parts, mix homogeneously, drip 3 parts 40% hydrogenperoxide steam generator, 45 DEG C of stirring reactions, stand, and decompression separated goes out ionic liquid, then by surplus materials sucking filtration, it is washed to neutrality, washing and drying, obtains the imidazoles-4-methyl formate based on ionic liquid.
After testing, the imidazoles-4-methyl formate based on ionic liquid that prepared by embodiment 1-7 is as follows with the result of the yield of the imidazoles-4-methyl formate of prior art and fusing point:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example | |
| Yield (%) | 81.4 | 86.5 | 83.2 | 84.1 | 82.9 | 83.5 | 84.6 | 73.1 |
| Fusing point (DEG C) | 155-158 | 156-158 | 159-161 | 158-162 | 158-160 | 156-159 | 159-161 | 156-160 |
As seen from the above table, the yield of imidazoles-4-methyl formate prepared by the imidazoles-4-methyl formate based on ionic liquid prepared by the present invention and traditional method is high, and fusing point is stable, but technique is simple, and cost is low, and therefore economic worth is good, is more beneficial for marketing.
Above-described embodiment is illustrative principles of the invention and effect thereof only, not for the restriction present invention. Above-described embodiment all under the spirit and category of the present invention, can be modified or change by any those skilled in the art. Therefore, art has usually intellectual such as modifying without departing from all equivalences completed under disclosed spirit and technological thought or change, must be contained by the claim of the present invention.
Claims (9)
1. the synthetic method based on the imidazoles-4-methyl formate of ionic liquid, it is characterised in that: comprise the following steps:
(1) in the there-necked flask with stirring and reflux, add ionic liquid and acetyl formic acid methyl ester, constant temperature stirs, it is slowly added dropwise Sodium ethylate when condensing reflux, constant temperature stirs, and adds Methanamide and sulphuric acid, and heated and stirred is to having reacted, it is cooled to room temperature, obtains intermediate product;
(2) intermediate product step (1) prepared adds alcoholic solution, mix homogeneously, dropping hydrogenperoxide steam generator, stirring reaction, stand, decompression separated go out ionic liquid, then by surplus materials sucking filtration, be washed to neutrality, washing and drying, obtain the imidazoles-4-methyl formate based on ionic liquid.
2. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (1), ionic liquid is hydrophobic type ionic liquid.
3. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (1), ionic liquid is alkyl-quaternaryammonium cations or the pyridylium of N-alkyl replacement.
4. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (1), the temperature of constant temperature stirring is 6-10 DEG C, and the time is 30-90min.
5. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (1), the temperature of heated and stirred is 100-110 DEG C, and the time is 2-4h.
6. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterized in that: in described step (1), the volume ratio of ionic liquid, acetyl formic acid methyl ester, Sodium ethylate, Methanamide and sulphuric acid is 5-8:2-4:1-2:2-3:1-3.
7. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (2), intermediate product, ethanol, hydrogenperoxide steam generator volume ratio be 1:3-6:2-4.
8. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (2), the concentration of hydrogenperoxide steam generator is 30-50%.
9. the synthetic method of a kind of imidazoles-4-methyl formate based on ionic liquid according to claim 1, it is characterised in that: in described step (2), the temperature of stirring reaction is 45-50 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892557A (en) * | 2019-05-05 | 2020-11-06 | 石家庄圣泰化工有限公司 | Synthetic method of piperazine film-forming ionic liquid |
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| CN101693694A (en) * | 2009-10-14 | 2010-04-14 | 苏州凯达生物医药技术有限公司 | Preparation method of glyoxaline formic ether and derivative thereof |
| CN102643237A (en) * | 2012-02-20 | 2012-08-22 | 武汉理工大学 | Method for preparing 1H-imidazole-4-formic acid |
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2016
- 2016-03-01 CN CN201610113398.9A patent/CN105646364B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101693694A (en) * | 2009-10-14 | 2010-04-14 | 苏州凯达生物医药技术有限公司 | Preparation method of glyoxaline formic ether and derivative thereof |
| CN102643237A (en) * | 2012-02-20 | 2012-08-22 | 武汉理工大学 | Method for preparing 1H-imidazole-4-formic acid |
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| 岳智洲等: "钨酸钠催化制备1H-咪唑-4-甲酸", 《化学试剂》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892557A (en) * | 2019-05-05 | 2020-11-06 | 石家庄圣泰化工有限公司 | Synthetic method of piperazine film-forming ionic liquid |
| CN111892557B (en) * | 2019-05-05 | 2022-11-08 | 河北圣泰材料股份有限公司 | Synthetic method of piperazine film-forming ionic liquid |
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